Single bath chrome dyeing process



Patented Dec. 19, 1950 SINGLE BATH CHROME DYEING PROCESS USING AZO DYES HAVING NAPHTHOL- SULFONAMIDE GROUPS Willy Widmer, Bottmingen, Alphonse Heckendorn, Basel, and Emil Mannhart, Riehen, Switzerland, assignors to Ciba Limited, Basel, Switzerland, a Swiss firm N Drawing. Application September 6, 1949, Se-

rial No. 114,291. In Switzerland September 29,

7 Claims.

represents the radical of a 2-hydroxynaphthalene sulfonic acid amide bound in the l-position to the azo linkage, and in which X and Y each represent a hydrogen atom or an alkyl or hydroxalkyl group and together contain not more than 8 carbon atoms, by conducting the dyeing by the single bath chroming process with a solution containing the dyestuff and an agent yielding chromium.

The monoazo-dyestufis used in the present invention, and of which some are known, may be prepared, for example, by coupling an orthohydroXy-diazo-compound of the benzene series with a Z-hydroxynaphthalene sulfonic acid amide of the general formula benzene series serving as starting materials and obtainable from the corresponding amines may contain a wide variety of further substituents with the exception of carboxylic acid and sulfonic acid groups. As such substituents there may be mentioned, for example, alkyl groups such as ethyl or methyl groups, alkoxy groups such as ethox'y or methoxy groups, acy-lamino groups such as acetylami-no groups-, or halogen atoms such as bromine and especially chlorine atoms. Especially valuable dyestufis are obtained from ortho hydroxy diazo compounds containing nitro groups, and above all from diazotised 4- or 5-nitro-2-a-mino-l-hydroxybenzene or 'diazotised 4-chloro-5-nitro-2-amino-1-hydroxybenzene.

As examples of such ortho-hydroxy-diazocompounds of the benzene series there may be mentioned those obtained from the following amines:

4 methyl e 2 amino-l-hydroxybenzene, 4- chloro-2-amino-l-hydroxybenzene, 2-amino-1- hydroxybenzene 4 sul'fonic acid N-isopropylamide, 3-, 4-, 5- or fi-nitro-z-amino-l-hydroXy-. benzene, 4: S-dinitro-Z-amino-l-hydroxybenzene,

4 nitro 6 acetylamino-Z-amino-l-hydroxybenzene, 5-nitroor 6-nitro-4-methyl-2-aminol-hydroxybenzene, 4-chloro-5-nitroor 6-nitroz-amino-l-hydroxybenzene, 6-chloro-4-nitro-2- amino-l-hydroxybenzen'e and 4-chloro-6-acetylamino-2-amino-l-hydroxybenzene. V

In the z-hydroxynaphthalene sulfonic acid amides also used as starting materials for preparing the monoazodyestufis the sulionic acid amide group may be present in the 3-, 4-, 5-, 6- or 7-position.

Especially valuable dyestuffs are obtained from 2-hydroxynaphthalene sulfonic acid amides 'in which the sulfonic acid amide group occupies one of the ,c-position's of the siX-membered ring of the naphthalene nucleus which does not'contain the hydroxyl group, for example, from 2-hydroxynaphthalene-'7-sulfonic acid amides and especially from 2 hydroxynaphthalene-G-sulionic acid amides.

The hydroxynaphthalene sulfonic acid amides contain the group X so,N

in which X and Y have the meanings given above. The symbols X and Y may represent unbranched or, if desired, branched alkyl or hydroxy'alkyl 3 groups or hydrogen atoms. X and Y may be identical or different from one another and may be united to form a ring. There come into consideration, for example, hydroxynaphthalene sulfonic acid amides in which the group may be any one of the following groups:

but especially NH2.

Such hydroxynaphthalene sulfonic acid amides are in part known. They can generally be prepared by methods in themselves known, for example, by subjecting the appropriate 2-hydroxynaphthalene sulfonic acid to the action of an acylating agent, such as para-toluene sulfonyl chloride, to produce an ester of the hydroxynaphthalene sulfonic acid, treating the latter with a phosphorus chloride, such as phosphorus pentachloride, to convert the SO3H group into an -SO2C1 group, then reacting the resulting sulfonyl chloride with ammonia or an amine of the formula and finally hydrolysing the ester by the action of an alkali.

The 2 hydroxynapthalene 6 sulfonic acid amides can also be prepared by reacting with ammonia or an amine of the formula 2 hydroxynaphthalene-l-carboxylic acid-6-sulphonyl chloride obtainable from Z-hydroxynaphthalene-l-carboxylic acid by the action of chlorosulfonic acid, and heating the product in a weakly alkaline medium to split off the very mobile carboxyl group in the l-position of the naphthalene ring.

As examples of hydroxynaphthalene sulfonic acid amides with which valuable dyestuffs for use in the process of this invention can be made, there may be mentoined: 2-hydroxynaphthalenel-sulfonic acid amide, 2-hydroxynaphthalenel-sulfom'c acid N-isopropylamide, 2-hydroxynaphthalene-7-sulfonic acid amide, 2-hydroxynaphthalene 7 sulfonic acid N-dibutylamide, Z-hydroxynaphthalene 6 sulfonic acid- N -n-octylamide, Z-hydroxynaphthalene 6 sulfonic acid N-fi-hydroxyethylamide, 2-hydroxynaphthalene-B-sulfonic acid N-dimethylamide, 2-hydroxynaphthalene-G-sulfonic acid N-methylamide and Z-hydroxynaphthalene 6 sulfonic acid N-isopropylamide. 2-hydroxynaphthalenefi-sulfonic acid amide is especially valuable.

The ortho-hydroxy-diazo-compounds of the benzene series are advantageously coupled in an alkaline medium with the hydroxynaphthalene G-sulfonic acid amide.

sulfonic acid amides. For example, the hydroxynaphthalene sulfonic acid amide may be dissolved in the necessary quantity of a solution of an alkali hydroxide, and then alkali carbonate added and the diazo-compound added to the resulting solution.

In accordance with the present invention the dyeing is conducted by the single bath chroming process with a solution containing both the dyestuff and an agent yielding chromium. As agents yielding chromium there are used preferably compounds of hexa-valent chromium. A dyeing process of this kind is, for example, that in which there is used a solution containing the dyestuff and also an alkali chromate, for example, sodium chromate or potassium chromate and an ammonium salt of strong mineral acid, such as ammonium chloride or preferably ammonium sulfate.

By the process of this invention there are obtained especially on wool, but also on artificial fibers of superpolyamides or superpolyurethanes, very valuable dyeings which are in general distinguished by very good properties of wet fastness and above all by a very good to excellent fastness to light. Especially valuable, for example, navy blue to black, tints can be produced by this invention with those dyestuffs which contain in the radical of the diazo-component a nitro group.

In some cases very valuable tints are obtained by the process of this invention from mixtures of two or more dyestufis of the kind defined above. Such mixtures can be obtained either by mixing the individual dyestuffs or, in the case, for example, of dyestuffs derived from the same coupling components and dilferent diazo-components, by diazotising a mixture of the different amines and/or by simultaneously coupling the different diazo-compounds with the coupling components.

The following example illustrates the invention, the parts and percentages being by weight:

A dyebath is prepared with 4000 parts of water, 2 parts of potassium chromate, 2 parts of ammonium sulfate, 10 parts of crystalline sodium sulfate and 4 parts of the dyestuff obtainable by coupling diazotised 5-nitro-4-chloro2-amino- 1-hydroxybenzene with 2-hydroxynaphthalene- 100 parts of well wetted wool are entered into the dyebath at 60 0., the temperature is raised to the boil in the course of 30 minutes, and boiling is continued for 45 minutes. There are then added 0.5 part of acetic acid of 40 per cent. strength and boiling is continued for a further 45 minutes. The wool is dyed a fast navy blue tint.

The new dyestuif used in this example may be prepared as follows:

22.3 parts of 2-hydroxynaphthalene-6-sulfonic acid amide are dissolved in 200 parts of water and 11.2 parts of potassium hydroxide and coupled in the presence of 20 parts of sodium carbonate at 0 C. with the diazo-compound obtained in the usual manner from 19 parts of 5- nitro 2 chloro 2 amino-l-hydroxybenzene. Coupling sets in immediately and is complete in 4 hours. The dyestufi formed is isolated by filtration, washed with dilute sodium chloride solution and dried. There is obtained a black powder which dissolves in hot water with a blue-violet coloration and in concentrated sulfuric acid with a red coloration.

In the following table is a list of other dyestuffs which also yield valuable dyeings of very in which It represents an aromatic radical of the benzene series which contains a 'hydroiryl group Dyestuff from- Diazo-component Coupling component 'lint of the (dyeing) 5-Nitr0-2-amino-l-hydroxybenzene, 4:6-Dinitro-2-amino-l-hydroxyb enzene 4-Nitro-2-amino-l-hydroxyb enzene 6-Chloro-4-nitro-2-amin0-1-hydroxybenzene fi-Nitro-4-chl0ro-2-amino-l-hydroxybenzene 2-Hy1droxynaphthalene-fi-sulfonic acid amide. i o

bluish black. reddish black. black.

dark brown. reddish black. black.

do 5-Nitro-2-amino-l-hydroxybenzenc 2-Hyd5oxynaphthalenc-6-snlfonic acid methylami 4-Nitro-2-arnino l-hydroxybenzene 6-Chloro-4-nitro-2-arnino-1-hydroxybenzone l 5-Nitro4-chloro-2 amino l hydroxybenzcne 4-Ni]t)ro-2-amino-1-hydroxybenzene o e. 2-Hyd5oxynaphthalene-fi-sulfonic acid dimethylm e. 2-Hydroxynaphthalcne-6-sulfonic acid B-hydroxyctbylamide.

-.,do 2-Hyidroxynaphthalene-7-sulfonic acid amide. o 2-Hydroxynaphthalene-4-sulfonic acid amide reddish black.

black.

dark-brown-black. greenish navy blue.

ac dark black-brown.

A very valuable deep black dyeing is obtained by using in the manner described in the first paragraph of this example, instead of 4 parts of the dyestufi specified, a mixture consisting of 3 parts of the dyestufi from diazotised 5-nitro-2- amino-l-hydroxybenzene and 2-hydroxynaphthalene-G-sulfonic acid amide and 1 part of the dyestuif from diazotised 4-nitro-2-amino-1-hydroxybenzene and 2-hydroxynaphthalene-6-sulfonic acid amide.

What we claim is:

1. A process for producing fast dyeings, which comprises conducting the dyeing by the single bath chroming process with a solution containing an agent yielding chromium and a monoazodyestufi which is free from carboxylic acid and sulfonic acid groups and corresponds to the general formula in which R represents an aromatic radical of the benzene series which contains a hydroxyl group in ortho-position to the azo linkage, in which the radical SO2N occupies one of the B-positions of the six-membered ring of the naphthalene nucleus which does not contain the hydroxyl group, and in which X and Y each represents a member of the group consisting of a hydrogen atom, an alkyl group and a hydroxyalkyl group and together contain not more than 8 carbon atoms.

2. A process for producing fast dyeings, which comprises conducting the dyeing by the single bath chroming process with a solution containing an agent yielding chromium and a monoazo-dyestufi which is free from carboxylic acid and sulfonic acid groups and corresponds to the formula in ortho-position to the azo linkage.

3. A process for producing fast dyeings, which comprises conducting the dyeing by the single bath chroming process with a solution containing an agent yielding chromium and a monoazo-dyestuff which is free from carboxylic acid and sulin which R represents an aromatic radical of the benzene series which contains a hydroxyl group in ortho-position to the azo linkage and a nitro group.

4. A process for producing fast dyeings, which comprises conducting the dyeing by the single bath chroming process with a solution containing an agent yielding chromium and the monoazo dyestufi of the formula OH HC| OaN 5. A process for producing fast dyeings, which comprises conducting the dyeing by the single bath chroming process with a solution containing so an agent yielding chromium and the monoazo dyestuff of the formula 6. A process for producing fast dyeings, which comprises conducting the dyeing by the single 5 bath chroming process with a solution containing an agent yielding chromium and the monoazo dyestuff of the formula OH HO NH2 0 o '7. A dyebath containing an agent yielding chromium and a monoazo-dyestufi which is free from carboxylic acid and sulfonic acid groups and corin which R represents an aromatic radical of the benzene series which contains a hydroxyl group in ortho-position to the azo linkage, in which the radical x -SO2N/ occupies one of the p-positions of the six-membered ring of the naphthalene nucleus which does not contain the hydroxyl group, and in which X and Y each represents a member of the group consisting of a hydrogen atom, an alkyl group and a hydroxyalkyl group and together contain not more than 8 carbon atoms.

WILLY WlDMER. ALPHONSE HECKENDORN. EMIL MANNHART.

REFERENCES CITED The following references are of record in the file of this patent:

UNITED STATES PATENTS Number Name Date 2,122,127 Benade June 28, 1938 FOREIGN PATENTS Number Country Date 232,870 Switzerland Aug. 16, 1944 OTHER REFERENCES Theory and Practice of Wool Dyeing, by C. L.

Bird, published by Society of Dyers and Colourists, 32/34 Picadilly Bradford, 1947, page 87. 

1. A PROCESS OF PRODUCING FAST DYEINGS, WHICH COMPRISES CONDUCTING THE DYEING BY THE SINGLE BATH CHROMING PROCESS WITH A SOLUTION CONTAINING AN AGENT YIELDING CHROMIUM AND A MONOAZODYESTUFF WHICH IS FREE FROM CARBOXYLIC ACID AND SULFONIC ACID GROUPS AND CORRESPONDS TO THE GENERAL FORMULA. 